PURE β-ANTHRAQUINONYL-UREA-CHLORID AND PROCESS OF MAKING SAME.



UNITED* STATES PATENT QFFICE,

ALBRECHT SCHMIDT AND GEORG- KRPLNZLEIN, OFIHUCHST-OLLTHE-MAIN, GERMANY,

ASSIGNORS TO FARBNERKE "VORIVZ. MEISTER IIUCIUkl 85 BRfi'NING, OF I5OHST-0N- THE-MAIN, GERMANY, A CORPORATION OE GERMANY,

PURE fl-ANTHRAQUINGNYL-UREA-CHLORID AND PRUGESS OF MAKING SAME.

No Drawing.

Specification of Letters Patent.

Application filed May 11, 1910. Serial No. 560,736.

Patented Sept, 10, 191%.

To all whom it may concern:

Be it known that We, Annancn'i SCHMIDT, Ph. D, chemist, and G'I-IQRG KRKNZLEIN, Ph. 1)., chemist, citizens of the Empire of Germany, residing at Hochston-the-l\riain, Germany, have invented certain new and useful Improvements in a Pure fi-Anthraquinonyl-Urea-Chlorid and Process of Making Same, of which the following is a specification.

@- antluaquinonyl urea chlorid and s mode of preparing it in a pure state have urea chlorid at all if; obtainable from c-ami-- noanthraquinone. Homever, according to the surprising discovery We have made, {5- anthraquinonyl-urea-chlorid as such can be produced from fisaminoanthraquinone by a reaction which, in View of the behavior of +Cl.CO.Cl-

As the mixture expected to result from the above reaction, consisting of tl-ant-hraquinonyl-urea-chlorid, insoluble or difiicult-ly soluble in indifferent solvents, and of insoluble hydrochlorid of aminoanthraquinone, mot be separated, it was accordingly not possible to obtain in this manner a pure urea-chlorid. This is indeed the case under ordinary conditions. We have found that it, for instance, phosgen is introduced into a suspension of {5-21i'ninoanthraquinone in toluene in the cold, or if a suspension of (3- aminoantbraquinone in benzene is added to other bases, may be regarded as abnormal, and'cnlv under conditions which could not be fol .non. iiccording to what is the case with aromatic amins, it was to be expected that by the action of phosgen on aminoanthraquinones no pure anthrsquinonyl-urcnchlorids, but instead mixtures of them with the hydrochlorids of aniinoanthraquinones, would be obtained, that is to products of no technical value. This, as has been proved, is indeed at first the case With aininoanthraquinone, if certain conditions are not observed in the case of or-aniinoanthraquinone the reaction is of a still more complicated nature), As is known, by the action of phosgen upon nniins, for instance diphcnylainin, dinaphthylnmin, phonetidin and the like, there is always produced a moleculammixturc partly of urea-chlorid and partly of hydrochlorid of aniin. For instance on causing phosgcn to not upon diphenylamin (compare Bar. 9, 396, Ball. dc Zn docit Ulzz'miquc, new series 25, 251) the reaction is as follows:

As is known, this is a typical reaction (compare also Ber. 23, 428 dinaphthyl-vureachlorid). If applied to the ffi-aminoanthraquinone, the reaction should be as follows:

asolution of phosgen in benzene, a mixture is obtained, consisting of hydrochlorid of (fi-aniinoanthraquinonc and uren-chlorid, which cannot be separated by any solvent and Which is therefore unsuitable for a number of reactions.

By means of the cl vcst-ufl' obtainable from the pure [fi-anthraquinonyl-urea-chlorid and anilin itis possible to ascertain the above mentioned rcsult ot' the reaction. If, for instance, the aforesaid mixture, consisting of hydrochlorid of fi-aminoanthraquinone and {5-anthraquinonyl-ures-chlorid is treated with anilin, a mixture, of no technical value, of {i-anthraquinone with B-anthraquinonylhenyl-urea is obtained. This mixture can e recognized as such, upon recrystallizing 5, it in a larger quantity of mtrobenzene;

-moreover it can be ascertained by reducing" 7 'iiollowing new and uniform conditions: I qfiwwe have ,ioundvthat the hydrochlorid of aminoanthraquinone will gradually disapjpear iromthejnitial reaction-mass, if ghosgenie-caused to act. upon it in the col un- .tijlthere is no furtherescape of hydrochloric QB-acid, particularly if an excess used, or \by causing phos on to act upon it in a gentle heat which faci 'tates'the reaction; we have furthermore ascertained that alsolby the actien of phosgen upon aqsuspension of hydrochlorid of fi-aminoanthraquinone in nitrobenzene (less promptly in toluene) {i-anthraquinonyl urea-chlorid is adually formed with gradual liberation of ydrochloric acid. Consequently the process consists of the following operations: Phosgen is caused to act upon B-aminoanthraqu'inone or hydrochlorid of B-aminoanthraquinonelfor so long a time and under such conditions'that the hydrochlorid of fi-aminoanthraquinone disappear entirely or at least for a greater part from the reaction mass, which can be easily ascertained by a test in working it up into anthraquinonyl-phenyl-urea. The reaction is eflected either by a prolonged action of phosgen, advantageously with an excess, upon (i-aminoanthraquinone in the cold (preferably for instance in a suspension of mtrobenzene), or by using phosgen, advantageously with a slight excess, in a gentle heat, also preferably for instance in a suspension of nitrobenzene. In the event of .l V gently heating, the temperature must not be allowed to rise so high that 5-[5 dianthraquinonyl-urea forms; thus', for instance, a temperature of about 100 C. may still be used. Consequently a slight excess or almost the theoretical quantity of phosgen will suffice if phoa n is caused to act upon (i-aminoanthraquinnne preferably in nitrobenzene in the heat, for instance attemperatures of from 40 to about 120 C. This is also a quite surprising fact, because it could not to be expected that a {i-anthraquinonylurea-chlorid possesses such a stability.

65 Example 1:A large excess of phosgen is introduced while stirring into a cold suspension of 200 grams of [i-aminoanthraqulnone in 2 kilosof nitrobenzene and the st1r ring is continued until a filtered test, on treatment with -anilin, yields fi-anthraqm- 7G 'nonyl-phenyl-urea, dyeing pure yellow tlnts' The grayish-white product thus obtained s filtered off, Washed with carbon tetrachlorld and dried in 'LlCLtO. I

Example II: A little more than the calculated quantity of phosgen is introduced in the course of several hours into a suspension of 200 grams of Q-aminoanthraquinone in 2 kilos of nitrobenzeneatabout 50 C. while stirring, preferably under. slight pressure. The filtered ofl product .which is washed with carbon tetrachlorid is pure.

Found: 9D Cl=-12.

Calculated for 01-122;

N= as 0 The new product is a gray powder which when heated with anilin yields (i-anthra- I uinon l- 'henyl-urea of the composition 97, 11 1 1 8 soluble in concentrated sulfuric acid with a yellowish color.

For further workin up the urea chlorid it isnot necessary to iso ate the same, but the mass obtained can be immediately worked up by previously removing the slight excess of phosgen and the hydrochlorid acid by means 0 a dry current of air.

- If instead of nitrobenzene, for instance toluene is employed, the conversion into urea-chlorid occurs considerably more slowly and is generally terminated only after 20 hours.

Having now particularly des ribed our invention, what we claim is:

,1. As a new product, fi-anthrauinonylurea-chlorid in a pure state free rom hy-' drochlorjid of {B-aminoanthraquinone, being a gray powder which when heated with anilin y elds 6-anthraquinonvl-phenyl-urea of the composition C H N O soluble in concentrated sulfuric acid with a yellowish color.

2. The process of manufacturing fi-anthraquinonyl-urea-chlori'ds in a pure state free from hydrochlorid' of b-aminoanthraquinone, which consists in causing phosgen to act upon (B-aminoanthra'quinone, in the presence of a solvent until the hydro'chlorid of 0- aminoanthraquinone, which forms first, has 12-" disappeared I from the reaction-mass, and hais changed into B-anthraquinoneurea-chlor1 3. The process of manufacturing B-anthraquinonyl-urea-chlorids in a pure state free from hydrochiorid of B-amino-anthraqui- In testimony whereof, We aflix 0m signanonc, which consists in causing phosgen to tures iii presence 0f two witnesses. act upon B-aminonuthmquiuone ii the pres- ALBREGHT SCHMIDT ence ()f 8. solvent at temperatures of from GFQPG Y :iN I-F N 5 40 0 190 (1., until the l'iydrochlorid of J amine-zu1tlnaquinone, which forms first, has Vitncsses: disn ivpoared from the reaction-muss, and has BERNILARD Lmmaclimz,

changed into 5-2111thruquinone-ui'ea-chloridl OTTO Rumemmws. 

